Ammonium Chloride → (3RS,4RS)-7-methoxy-3-(4-methoxyphenyl)-4-(2-propenyl)-3-propylthiochroman

HRID 1267780Notes

Reaction equation

HRID 1267780 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([C:7](=O)[C:8]([C:16]3[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=3)([CH2:13][CH2:14][CH3:15])[CH2:9][S:10]2)=[CH:5][CH:4]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl-].[NH4+].[CH2:33]([Si](C)(C)C)[CH:34]=[CH2:35]>O1CCCC1.ClCCCl.[I-].[Zn+2].[I-].O>[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH:7]([CH2:35][CH:34]=[CH2:33])[C:8]([C:16]3[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=3)([CH2:13][CH2:14][CH3:15])[CH2:9][S:10]2)=[CH:5][CH:4]=1

Participants

9

Reactant 4

HCID 25517Ammonium ChlorideHCID 69808AllyltrimethylsilaneHCID 18546285HCID 18546285, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 18546273(3RS,4RS)-7-methoxy-3-(4-methoxyphenyl)-4-(2-propenyl)-3-propylthiochromanYield 72.2%

Reagents, catalysts & solvents 4

HCID 9883512zinc(II)iodideCatalystHCID 111,2-DichloroethaneSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 7-methoxy-3-(4-methoxyphenyl)-3-propylthiochroman-4-one (1.7 g, 4.96 mmol) in anhydrous tetrahydrofuran (30 ml) was cooled to −78° C. Lithium aluminum hydride (94.2 mg, 2.48 mmol) was added to this solution, followed by stirring for 12 hours at room temperature. Saturated aqueous ammonium chloride (100 ml) was added to the reaction mixture, which was then extracted twice with ethyl acetate (100 ml). The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, zinc iodide (1.9 g, 5.95 mmol) and allyltrimethylsilane (1.57 ml, 5.95 mmol) were added dropwise to a solution of the residue in 1,2-dichloroethane (50 ml) at 0° C., followed by stirring for 12 hours at room temperature. Water was added to the reaction mixture, which was then extracted twice with dichloromethane. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent:ethyl acetate/hexane=1/90) to give (3RS,4RS)-7-methoxy-3-(4-methoxyphenyl)-4-(2-propenyl)-3-propylthiochroman (1.32 g, Yield 72%).

Workup

  1. extractionwas then extracted twice with ethyl acetate (100 ml)
  2. washThe combined organic layers were washed with water and saturated aqueous sodium chloride
  3. dry with materialdried over anhydrous magnesium sulfate
  4. stirringby stirring for 12 hours at room temperature
  5. extractionwas then extracted twice with dichloromethane
  6. washThe combined organic layers were washed with water and saturated aqueous sodium chloride
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationAfter distilling off the solvent
  9. customthe residue was purified by silica gel column chromatography (eluent:ethyl acetate/hexane=1/90)

Sources & evidence

ORD record
ord-0b008a8629c54ac7bf266a2b976ae13b
Source dataset
uspto-grants-2003_04
Patent number
US06552068B1

Reaction notes

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